Phosphaarsenes - Combining Phospha- and Arsa-Wittig-Reagents.

Dipnictenes of the type RPn=PnR (Pn=P, As, Sb, Bi) can be viewed as dimers of the corresponding pnictinidenes R-Pn. Phosphanylidene- and arsanylidenephosphoranes (R-Pn(PMe 3 ); Pn=P, As) have been shown to be versatile synthetic surrogates for the delivery of pnictinidene fragments. We now report that thermal treatment of 1 : 1 mixtures of R-P(PMe 3 ) and R'-As(PMe 3 ) gives access to arsaphosphenes of the type RP=AsR'. Three examples are presented and the properties and reactivity of Mes*P=As Dip Ter (1) (Mes*=2,4,6-tBu 3 -C 6 H 2 ; Dip Ter=2,6-(2,6-iPr 2 C 6 H 3 ) 2 -C 6 H 3 ) were studied in detail. Solid state 31 P NMR spectroscopy revealed a large 31 P NMR chemical shift anisotropy with a span of ca. 920 ppm for 1 while computational methods were employed to investigate this pronounced magnetic deshielding of the P atom in 1. In the presence of the carbene IMe 4 (IMe 4 =:C(MeNCMe) 2 ) 1 is shown to be split into the corresponding NHC adducts Mes*P(IMe 4 ) and Dip TerAs(IMe 4 ), which is additionally shown for diarsenes.